Angle Dispersive X-ray Diffraction Beamline
(BL-12) for Materials Research
A. K. Sinha (anil@rrcat.gov.in)
Indus Synchrotron Utilisation Division (ISUD)
Raja Ramanna Center for Advanced technology
Indore, India
Acknowledgements
ISUD Colleagues
Plan of Talk
1. Introduction (Creating Synchrotron Radiation)
2. Angle Dispersive X-ray Diffraction beamline
3. Applications of the beamline for Materials
Research (Some Results)
Creating Synchrotron Radiation
SR Properties
SR Spectrum
• broad spectral range
– X-rays-VUV-visible & beyond
• highly collimated
– ~ milli-radian divergence
•
•
•
•
very high flux and brightness
linear polarization
calculable characteristics
Time structure
Ec (keV )  0.665BE 2
Flux  photons/sec/mrad/0.1% BW
brightness  Flux/ mm2/mrad2
Schematic View Of Indus Complex
TL-1
Microtron
(20 MeV)
TL-2
TL-3
Indus-2, 2.5 GeV
SRS
Indus-1
(450 MeV)
Optical Layout of ADXRD beamline
(top view)
(side view)
Advantages of using adaptive optics
1. Various operation modes of the beamline
1. High energy resolution , low flux mode
(collimated mode)
2. High energy resolution, moderate flux mode
2. The photon beam can be focused at desired
point making it convenient for use of multiple
experimental stations
Measured beamline specifications
Range:
Energy resolution (E/ΔE):
Flux: @2.5GeV, 100mA :
Beam size :
5 – 20 keV
8000 (at 8keV)
3x 10 9 ph/sec (at 11 keV)
0.7mm(h) x 0.5 mm(v)
Applications
Powder X-ray Diffraction
Single Crystal Diffraction
X-ray absorption spectroscopy
XRD at extreme conditions
Low Temperature XRD (3K – 400K)
High Temperature XRD (900K)
High pressure XRD
Photograph of the beamline in radiation hutch
EXPERIMENTAL STATIONS
Six circle diffractometer with
scintillation detector
Angular resolution:
Powder Sample:
0.015 degree
(sigma in 2 theta)
Single Crystal:
14 arc sec (FWHM)
Image plate area detector
Angular resolution:
Powder Sample:
Time taken for
one pattern:
0.03 degree
(sigma in 2 theta)
Few Minutes
EXPERIMENTAL STATIONS
Powder diffraction at the image
plate area detector
Powder diffraction at the
Diffractometer
I / Io (normalised )
1.0
Sample : LaB6 ( nist )
DCM Energy : 11.0 keV
0.8
0.6
0.4
0.2
0.0
19
th
10 15 20 25 30 35 40 45 50 55 60 65 70
M ay 10

L a B 6 P o w d e r w ith I m a g e P la te
P la te d is ta n c e : 2 0 0 m m
N o . o f P ix e l s : 2 3 0 0 X 2 3 0 0
P ix e l S iz e
: 150X 150m
20000
Counts/Pixel
IR 37m A , 2G eV ,
15000
D C M E n erg y 14 keV
F itte d E n e r g y 1 4 .4 5 k e V
Powder diffraction at the diffractomer
with scintillation detector
10000
5000
0
5
10
15
20
25
2
30
35
40
AIP conf proc. 1349 (2011) 503
J. Phys.: Conf Series 425, 072017(2013)
Applications of the beamline
• X ray Diffraction (XRD)
• Anomalous XRD
• X-ray Absorption Near Edge Structure (XANES)
• High Pressure XRD
• Low temperature XRD
• High Temperature XRD
Applications of ADXRD beamline
X-ray Diffraction
Single Crystal
Polycrystalline
Amorphous
Bulk
Powder
Thin Film
Bulk
Epitaxy
X-ray Diffraction
Normal omega –
2theta scan
Grazing incidence XRD
Anomalous XRD
X-ray Diffraction under extreme conditions of temperature and pressure
Applications of the beamline
•Single Crystal Diffraction
•Powder diffraction
•Amorphous phase scattering and RDF
•Anomalous XRD
•X-ray Absorption Near Edge Structure (XANES)
• High Pressure XRD
• Low temperature XRD
Applications of the beamline
1. Single crystal diffraction
J. Crystal Growth 351
(2012) 88.
(a) Rocking curve for (4 2 2) plane of 0.1 mole% Tl doped CsI and (b) 2ϴ position of same plane. (energy- 9750 eV).
with Al absorber
180000
(400)
6000
160000
Intensity (arb. unit)
140000
4000
2000
(600)
Intensity (arb Units)
16.66
Appl. Optics,
50 (2011) 6006.
120000
100000
80000
60000
40000
25.09
20000
0
0
15
20
25
2
30
35
8.30
8.35
8.40
8.45
8.50

(a) ϴ-2ϴ scan for (100) plane of monoclinic Ga2O3 single crystal (b) Rocking curve of the (400) peak of (100) plane
GaP epitaxial layer on Ge (111)
150000
175 C
layer peak scan only (RT)
100000
120000
1000
Intensity (AU)
Intensity (AU)
10000
full scan RT
100
90000
60000
30000
10
0
1
60
61
62
63
64
(2 theta)
61.8
62.0
62.2
62.4
62.6
62.8
63.0
63.2
63.4
63.6
63.8
2 Theta
GaP (111) grown on Ge (111) substrate.
Full (444) scan shows Ge and GaP peaks.
Two domains with 60 degree angle between them
High temperature shift in peak may be because of change in lattice parameter and
Strain.
2. Powder Diffraction
X-ray diffraction studies of Gd1-xCaxBaCo2O5.5 system (0  x  0.30)
The crystal structure of
GdBaCo2O5.5 from the
refined values of lattice
and
structural
parameters
obtained
from
the
Rietveld
refinement of XRD data
obtained
at
ADXRD
beamline.
J. Appl. Phys. 113 (2013) 104101
2. Powder Diffraction
10
20
30
2 theta
40
obs_500C
cal
obs-cal
Intensity(A.U.)
Intensity(A.U.)
obs_800C
cal
obs-cal
10
50
20
30
40
50
2 theta

5
10
15
20
25
2 theta
30
35
40
obs_300C
cal
obs-cal
Intensity(A.U.)
Intensity(A.U.)
obs_as grown
cal
obs-cal
45

10
20
30
40
50
2 theta
Multi-phase Rietveld refinement of various phases of
coblat oxide nanoparticles
J. Phys. and Chem. of
Solids 75 (2014) 397
The XRD data along with the Rietveld
fitting
of
relaxor
ferroelectric
[Pb(Mg1/3Nb2/3)O3] obtained on the Angle
dispersive XRD beamline (BL-12)
2. Powder Diffraction (Nano-particles)
Image Plate data
Williamson-Hall Plot
Powder XRD on Cobalt oxide nanoparticles
(β measured)2 = (β instrumental)2 + (β strain)2 + (β size)2
Β (strain) = 2. ε. tanθ
(220)
(111)
(111)
(220)
(222)
(400)
(311) CoO
(511) (440)
(422)
Β (size) = (0.9 x λ)/(D cosθ)
900
Mixed
2.4
800
Co3O4
400
Co3O4
350
Co3O4
10
30
20
Microstrain (%)
Intensty (AU)
(311)
(220)
900
2.0
1.6
1.2
40
Angle (2)
0.8
14
16
18
20
22
24
Particle size (nm)
Appl. Phys. A 108 (2012) 607
26
28
30
3. Amorphous phase scattering and RDF
7000
120
6000
100
5000
RDF(r)
Intensity(I(q))
80
4000
3000
60
40
2000
1000
2
k.bcoh
2
k.bcoh.S(q)
2
2
k.bcoh+k.bincoh
20
0
0
2
4
6
8
q(1/)
1.
2.
3.
4.
5.
6.
0
0
2
4
6
8
10
r(A)
Take XDR data with highest possible q range
Correct the data for absorption correction, correction for sample holder etc
Normalize the such that I(q) = 1, at q tending to infinity and I(q) = S (0) at q = 0
S(0) may be calculated by thermodynamic limit
This gives static structure factor (S(q)).
FT of S(q) gives Radial distribution function (RDF), which is the atomic
distribution of atoms in real space
J. Appl. Phys. 111 (2012) 113518.
J. Alloys and Compounds (2014), In Press
Measurement (2014), In Press
4. X-ray absorption spectroscopy (XANES)
Information
1. Oxidation state of selected atom in a
compound
2. Electronic energy levels
3. Geometry of at atom in the lattice
I = Io x exp (- abs.t)
Measurement Modes
1. Transmission
2. Fluorescence
3. Photoelectron yield
Io IC1 S I IC2
Energy dispersive
detector
4. XANES
XANES at Cu edge
XANES at Cr edge
Intensity (arb. units)
10000
x=0.15
x=0.10
5000
x=0.05
A
0
5980
6000
6020
6040
Energy (eV)
(Na0.5Bi0.5TiO3)(1-x)(BiCrO3)x
J. Mat. Sci. 47 (2011) 2011
Fe72.9Cu0.9Nb3.1Si13.1B8.9 (Finemet)
J. Appl. Phys. 110 (2011) 933537
4. XANES
11520
160000
11540
11560
11580
11600
11620
11580
11600
11620
140000
Pt K-edge XANES
Intensity (AU)
120000
100000
80000
60000
40000
20000
0
11520
11540
11560
Photon nergy eV)
The relative intensities and position of
Eu2+ and Eu3+ states were determined
by fitting XANES spectra with a two
component model consisting of an
arctangent step function and a
Lorentzian peak for each valence state.
From fitting, the valence state
population for Eu2+ is about 82%
Phys. Rev. B. (2012) 00510
J. Appl. Phys. 113 (2013) 104101
5. Anomalous XRD
2000
1000
0
-1000
Diffraction intensity (AU)
Intensity (AU)
3000
500
Diffraction peak intensity (AU)
7702eV
7704 eV
7706 eV
7708 eV
7710eV
7712eV
7714eV
7716eV
7718eV
7720eV
7722eV
7724eV
7726eV
7728eV
7730eV
7732eV
7734eV
7736eV
7738eV
600
400
400
300
7.64
7.68
200
0
7.64
7.68
7.72
Photon Energy (KeV)
10
20
30
40
7.72
7.76
Photon Energy (keV)
50
2 (degrees)
DANES in Cobalt oxide nanoparticles
7.76
Normalised XRD Intensity (Arb. units)
5. Anomalous XRD
GaAs single crystal
10300
10400
10500
Photon energy (eV)
Normalized XRD intensity for Ga
ended (blue) and As ended (red)
faces of GaAs single crystal.
The (100) superlattice reflection, obtained
using anomalous XRD at 7112 eV (Fe Kedge), is indicative of ordered structure.
J. Appl. Phys. 111 (2012) 113518
6. High pressure XRD
HPXRD pattern of LaGa with Ag as an
internal pressure calibrant.
Phil. Mag. (2013)
http://dx.doi.org/10.1080//4786435.2013.826880
7. Low Temperature XRD Measurements
Liquid He based flow
type cryostat
 Temperature Range
- 3K – 450K
 PID Temperature
Controller (Lakeshore
331)
Temperature
≈ 0.15K
stability
XRD pattern for Ru doped LiMn2O4 at various )
temperatures between 289K and 200K showing
phase transition from Cubic to orthorhombic
phase.
Structural transition temperature as a function of
increasing Ru concentration
XRD pattern for BaTiO3
Thank You for your kind
attention